Alkanolamine sulfates of hydroxy ethers



Patented July 7, 1 953 UNITED STATES PATENT OFFICE ALKANOLALHNE SULFATES 01* HYDROXY ETHERS- Milton Kosmin, Dayton, Ohio, assignor to Monsanto Chemical Company, St. Louis, Mo., a corporation of Delaware No Drawing. Application April 16, 1951, Serial No. 221,319

s Claims. (01. 260-458) The present invention relates to. compounds having high surface-activity in aqueous solutions and to processes for preparing the said compounds.

In my copending applicationserial No. 179,384

filed August 14, 1950, I have disclosed alkali metal or ammonium sulfates of certain Z-butylobtanoll-ethylene oxide condensates. These products. are produced by condensing ethylene oxide with 2- butyloctanol-l, sulfating the condensate and neutralizing the resulting sulfated product with an alkali metal or ammonium hydroxide. While the alkali metal or ammonium salts thus obtained show very good detergency, they are not sufficiently soluble in water to permit the preparation of aqueous solutions having a concentration of more than, say, 50% of condensate. Hence they cannot be used for the preparation of liquid detergents of adequate sudsing properties.

-I have now found that if at least 3, but less than 11 moles of ethylene oxide be condensed fates there is obtained a series of water-soluble products which exhibits very good wetting-out and detergency properties. Concentrated aqueous solutions of the present products may be made to with Z-butyloctanol-l and the resulting hydroxy ethers are converted to certain alkanolamine sulyield liquid detergents of very good sudsing properties.

The present products are prepared bycondens- -ing ethylene oxide with'Z-butyloctanol-l until at least 3 moles, but not in excess of 11 moles; have been condensed with the alcohol and then sulfat ing and neutralizing the resulting condensation product with certain alkylolamines. The condensation may be carried out by mixing ethylene oxide either as gas or--1iquid with the alcohol and heating to a temperature or" from 110 to 170 C. The condensation reaction is aided by the presence of a catalyst. For this purpose any alka- 1 line materials, such as an alkali metal hydroxide or alcoholate may be used. The catalyst may be employed in relatively small'arnounts, usually 'from 0.5% to 1% being employed- Thecatalyst is added to the liquid alcohol at the beginning of the reaction. .Sulfation of the alcohol-ethylene oxide condensate may beefiected in known manner; for example, by reaction with dilute or con-' centrated sulfuric acid, oleum, sulfur trioxide, chlorosulfonic acid, etc. The sulfuric acid esters thus obtained are then neutralized, i. e., converted to salts by treatment with an alkanolamine having the general formula in which R is selected from the class consisting of hydrogen and the methyl radical and Y is selected from the class consisting of hydrogen an the radical Alkanolamines having the above general formula are ethanolamine, diethanolamine, triethanolamine, isopropanolamine, diisopropanolamine and triisopropanolamine.

The products so produced are alkanolamine sulfates of hydroxy ethers and are believed to have the'structure:

C zCHzCH2CH CHzCHzCHzCHzCHzCH: OH? H2 I (zHlohczH o-soalffllizHOH in which n is an integer having avalue'of at least 2, but not in excess of 10, R is selected from the class consisting of hydrogen and the methyl radical, and Yis selected from the class consisting of hydrogen and the radical The following examples will further illustrate 30 i this invention:

Example 1 145-150 C. during the progress of the reaction.

424 g. of this condensation product was dissolved in approximately 1300 ml. of liquid sulfur dioxide and to this there was added, dropwise,

i 123 g. of sulfur trioxide, at a temperature of from C. to C. and during a period of about 2 hours.

The resulting solution was then stirred until most of the sulfur dioxide had evaporated. 300 m1. of ethanol was then added and the whole was stirred under full water pump vacuum to remove sulfur dioxide. The product thus obtained consisted of an ethanol solution of the sulfatedtriethylene glycol ether of Z-butyloctanol-l.

scribed above.

sp'onded to the pentaethylene glycol ether of move the remainder of the sulfur dioxide.

A portion of the sulfated product obtained above was treated with monoethanolamine. The neutralized material was thendried in a stirred reactor at a pot temperature of 70-75 0113- mm. The dried product was the substantially pure monoethanolamine salt of sulfated triethylene glycol ether of Z-butyloctanol-l, a viscous liquid. It is designated as I-linthe tests reported in Example 3.

Neutralization of another portion of the sulfated triethylene glycol ether of 2-butyloctanol-l obtained above with dietha'nolaminaand' subsequent drying as above, gave the diethanolamine salt of sulfated triethylene glycol ether of 2-butyloctanol-l, a viscous liquid. This compound is designated as I-2 in tests reported in Example 3.

tergency of Gardinol WA, which is a commercial detergent produced by sulfating the alcohols de- '7 rived by hydrogenation of coconut oil fatty acids.

The detergency of the present products of Examples 1 and 2 and a related product as determined by the Harris method is illustrated in the following table:

Neutralization of still another portion of the sulfated triethylene glycol ether obtained above with "triethanolamine; and subsequent drying, gave the tr-iethanolamine salt of sulfated triethylene glycol ether of Z-butyloctanol-l, a. viscous liquid. This compound is designated'as I-3 in tests reported in Example 3.

Example 2 A portion of the Z-butyloctanol-l ethylene ox.-

idecondensation' product obtained in Example 1,

weighing 715 g., was further treated with 213 g.

of ethylene oxide using the same apparatus as de- The product obtained corre- 2-butyloctanol-1. 409 g. of this product was dissolved in approximately 1300 ml. of liquid sulfur dioxide, and to this there was slowly dropped 92 g. of sulfur trioxide, at a temperature of 55 C. and during a period of. about 2 hours. The sulfur dioxide was then evaporated from the reaction mixture by stirring at atmospheric pressure. 400 ml. of 95% ethanol was then added and stirring was" continued under water-pump vacuum to re- The product thus obtained was anethanol solution of 'sulfated pentaethylene glycol ether of 2'-butyloctanol-l.

Neutralization of a portion of this solution of the sulfated product with monoethanolamine and subsequent drying in a stirred reactor at a temperature of 60-65 C./13mm., for minutes gave the substantially pure monoethanolamine salt of sulfated pentaethylene glycol ether of 2-butyloctanol-l, a viscous liquid. It is designated as 11-1 in the tests reported in Example 3.

Neutralization of another portion of the sulfated material with diethanolamine and subse-- quent drying as above gave the substantially pure diethanolamine salt of sulfated pentaethylene glycol ether of 2-buty1octanol-1, also a viscous liquid. It is designated as 11-2 inthe tests reported in Example 3.

Still another portion of the sulfated material was similarly neutralized with triethanolamine and subsequently dried to yield the triethanolamine salt of sulfated pentaethylene glycol, designated as 11-3 in the tests of Example 3.

. Examples Relative detergency may be measured by any quantitative method; however for the purpose of evaluating the present and related products I have used the method described by Jay C. Harris in Soap and Sanitary Chemicals for August and September 1943. By the application of this method it is possible to evaluate the detergency For convenience I have compared the detergency of'the present and related products withthe de- 0f 8 product in terms of any standard detergent. 1

The builder consisted ot 40 parts of tetrasodium pyrophosphate, 40 parts of starch for each 20 parts of the active constituent.

The speed of wetting, as measured by the Draves test of the products of Examples 1 and 2 when dissolved in water to form solutions of the indicated concentrations gave the values shown below. Similarly obtained values for sodium 2-butyloctanol-l sulfate are included -for purposesof comparison;

Draves Wetting (Seconds at percent Concen- Product Tested Inst. 3.1 8. 8 37. 4 Inst. 3.8 11.1 35. 8 Inst. 4. 8 14. 6 53. 6 Inst. 4.4. 10.4 37.2 2. 5 5.0 14.1 46. 4 II-3 2.7 5.1 16.7 51.0 Sodium fibutyloetanol-l sulfate Inst. 4. 8 33. 6

Evaluation of the foaming properties of the products of Examples 1 and 2 as measured by the Ross-Miles lather test (proposed method of the American Society for Testing Materials) gave the following values:

Ross-Miles Lather Heights (cm.)

Product Tested 50 p. p. m. 300. p. p. m.

' At At Once 5 mm Once 5 What I claim is: l 1. Chemical compounds having the general formula in which n is an integer having a value of at least 2, but not in excessof 10, R is selected from the class consisting of'hydrogen and the in which R is selected from the class consisting of hydrogen and the methyl radical and Y is selected from the class consisting of hydrogen and the radical 3. Chemical compounds having the formula C 2CH2CH2CHa onaomomomomomoficm in which R is selected from the class consisting of hydrogen and the methyl radical and Y is selected from the class consisting of hydrogen and the radical CH2CHOH 4. The chemical compound having the formula omomomons 5. The chemical compound having the formula CHzCHzCHzCHa CHQCH2CHZCH2CHQCHZCH.CH2

($zH O )gC2H O-SO NHz(CH2CHzOH)z 6. The chemical compound having the formula CHQOH2OH2OH3 CHgCHzCHzCHzCHzCHzCIlCEh o lzH o )2C2H4O.SO3NH(CH2CH2OH)3 7. The chemical compound having the general formula CHzCHzCHzCH;

CHgCHzCHnCHzCHzCHz H.CH2

3zH4O )4021140 .50 gNHa. CHgCHzOH 8. The chemical compound having the general formula CHgCHzCHgCH:

CHsC HzCHgCHzCHnCHg H. CH2

($2H4O )4C2H4O .SO3NHz( CHzCHzO H):

NHLTON KOSMIN.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 1,970,578 Schoeller et a1. Aug. 21, 1934 2,174,761 Schuette Oct. 3, 1939 2,212,521 Harris 1 Aug. 27, 1940 FOREIGN PATENTS Number Country Date 810,382 France Mar. 20, 1937 

1. CHEMICAL COMPOUNDS HAVING THE GENERAL FORMULA 